Search

Three new D-π-A-structured organic dyes, coded as

Herein, an unprecedented report is presented on the incorporation of size-dependent gold nanoparticles (AuNPs) with polyvinylpyrrolidone (PVP) capping into a conventional hole transport layer, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). The hole transport layer blocks ion-diffusion/migration in methylammonium-lead-bromide (MAPbBr3)-based perovskite light-emitting diodes (PeLEDs) as a modified interlayer. The PVP-capped 90 nm AuNP device exhibited a seven-fold increase in efficiency (1.5%) as compared to the device without AuNPs (0.22%), where the device lifetime was also improved by 17-fold. This advancement is ascribed to the far-field scattering of AuNPs, modified work function and carrier trapping/detrapping. The improvement in device lifetime is attributed to PVP-capping of AuNPs which prevents indium diffusion into the perovskite layer and surface ion migration into PEDOT:PSS through the formation of induced electric dipole. The results also indicate that using large AuNPs (> 90 nm) reduces exciton recombination because of the trapping of excess charge carriers due to the large surface area.

SummaryWnt proteins regulate adult tissue homeostasis and repair by driving stem cell self-renewal and differentiation. High-performance Wnt preparations have enormous therapeutic potential, especially alongside various stem cell technologies. Currently, most of these Wnt preparations contain FBS or the detergent CHAPS to maintain Wnt solubility and activity. Recently, afamin was identified as a serum factor that solubilizes Wnt3a in conditioned media (CM), obviating the requirement for animal sera. Here, we report serum albumin (SA) is required for afamin-mediated solubilization of Wnt3a in CM. Moreover, SA-mediated solubilization of purified Wnt3a in tubes does not require afamin. This means conventional CHAPS-Wnt3a preparations can be modified into SA-purified Wnt3a (SA-pWnt3a) preparations by exchanging CHAPS for SA through dialysis. SA-pWnt3a preparations effectively promote the growth of human stem cell organoids. These data suggest SA as a physiological factor for maintaining Wnt3a activity in therapeutic applications.

As genomic analysis technology has advanced, it has become possible to sub-classify intrahepatic cholangiocarcinoma (ICC) at the histological or molecular level. However, there are no truly representative models of ICC subtypes for use in studying developmental differences, carcinogenesis, and personalized drug response. Here, we sought to develop ICC organoid models that reflect the phenotypic, molecular and genetic properties of the parent tumor, and performed integrative clustering of multiple genomic data—with subtype analysis—using these models. ICC organoids from 17 patients pathologically diagnosed with cholangiocarcinoma were prepared according to a previously established organoid culture protocol. ICC patients were subclassified into small-duct (SD) type and large-duct (LD) type according to histological characteristics and S100P, N-cadherin, and CD56 expression. ICC organoids were successfully established within one month and exhibited a morphology similar to that of their matching primary cancer. LD- and SD-type organoids exhibited histologic phenotypes and staining patterns characteristic of the corresponding ICC subtypes. ICC organoids showed high concordance of somatic mutations with primary tumors. Unsupervised principal component analysis clustering effectively separated each type of ICC. Differential gene expression revealed significant enrichment on KRAS, TGFβ and ERBB2 signaling pathways in LD-type compared with SD-type ICC (P P P = 0.0105). We successfully performed prospective modeling of histological subtype specification using patient-derived ICC organoids. Moreover, gene expression profiling of ICC organoids enabled identification of type-specific targetable pathways.

The co-facially stacked dyes on semiconductor films serve as an alternative model to elucidate the photo-driven exciton dynamics occurring in a molecular assembly. In this study, we report the unique emission properties of coumarin dye adsorbed on the surface of the semiconductor film, measured by ultrafast time-resolved fluorescence. When a rigid coumarin derivative, 7-hydroxycoumarin-3-carboxylic acid (OHCCA), is anchored on the Al2O3 film, the dye manifests dual emissions from the two lowest excited states. Various anchoring modes of a carboxylic acid group on the Al2O3 surface are invoked to account for the unusual emission process. Additionally, we identified characteristic transition dipole interactions in the well-stacked dye aggregates, which leads to discernible excitonic splitting in the electronic transitions. Femtosecond time-resolved fluorescence reveals that the excimer formation in the aggregate occurs with the time constant of 550 fs. Picosecond time-resolved emission spectra confirm the subsequent structural relaxations of the nascent excimer. The enhanced transition dipole via the electronic coupling between OHCCA and metal oxide can be responsible for the dual emission and the ultrafast excimer formation.

In this study, a

Objectives In the present study, the effects of sagittal split ramus osteotomy (SSRO) combined with intraoral vertical ramus osteotomy (IVRO) for the treatment of asymmetric mandible in class Ⅲ malocclusion patients were assessed and the postoperative stability of the mandibular condyle and the symptoms of temporomandibular joint disorder (TMD) evaluated. Materials and Methods A total of 82 patients who underwent orthognathic surgery for the treatment of facial asymmetry or mandibular asymmetry at the Department of Oral and Maxillofacial Surgery, Dong-A University Hospital, from 2016 to 2021 were selected. The patients that underwent SSRO with IVRO were assigned to Group I (n=8) and patients that received bilateral SSRO (BSSRO) to Group II (n=10, simple random sampling). Preoperative and postoperative three-dimensional computed tomography (CT) axial images obtained for each group were superimposed. The condylar position changes and degree of rotation on the superimposed images were measured, and the changes in condyle based on the amount of chin movement for each surgical method were statistically analyzed. Results Group I showed a greater amount of postoperative chin movement. For the amount of mediolateral condylar displacement on the deviated side, Groups I and II showed an average lateral displacement of 0.07 mm and 1.62 mm, respectively, and statistically significantly correlated with the amount of chin movement (P=0.004). Most of the TMD symptoms in Group I patients who underwent SSRO with IVRO showed improvement. Conclusion When a large amount of mandibular rotation is required to match the menton to the midline of the face, IVRO on the deviated side is considered a technique to prevent condylar torque. In the present study, worsening of TMD symptoms did not occur after orthognathic surgery in any of the 18 patients.

Herein, we employed a molecular Ru(II) catalyst immobilized onto TiO2 particulates of (4,4'-Y2-bpy)RuII(CO)2Cl2 (RuP; Y = CH2PO(OH)2), as a hybrid catalyst system to secure the efficient and steady catalytic activity of a molecular bipyridyl Ru(II)-complex-based photocatalytic system for CO2 reduction. From a series of operando FTIR spectrochemical analyses, it was found that the TiO2-fixed molecular Ru(II) complex leads to efficient stabilization of the key monomeric intermediate, RuII-hydride (LRuII(H)(CO)2Cl), and suppresses the formation of polymeric Ru(II) complex (-(L(CO)2Ru-Ru(CO)2L)n-), which is a major deactivation product produced during photoreaction via the Ru-Ru dimeric route. Active promotion of the monomeric catalytic route in a hetero-binary system (IrPS + TiO2/RuP) that uses TiO2-bound Ru(II) complex as reduction catalyst led to highly increased activity as well as durability of photocatalytic behavior with respect to the homogeneous catalysis of free Ru(II) catalyst (IrPS + Ru(II) catalyst). This catalytic strategy produced maximal turnover numbers (TONs) of >4816 and >2228, respectively, for CO and HCOO- production in CO2-saturated N,N-dimethylformamide (DMF)/TEOA (16.7 vol % TEOA) solution containing a 0.1 M sacrificial electron donor.

Tubby mice exhibit hearing impairment due to the loss of stereocilin from the tip regions that connect the tallest stereocilia of the outer hair cells (OHCs) to the tectorial membrane. Stereocilin is an essential stereociliary protein in the OHCs, the mutation of which in humans causes autosomal recessive non-syndromic deafness. Map1a is a modifier of tubby hearing (moth1), and its wild-type allele, rather than the moth1 allele from the C57BL/6 J strain, restores stereocilin localization to the stereocilia and rescues the hearing impairment of tubby mice. The mechanism by which MAP1A accomplishes this is unclear, partly due to ambiguity regarding whether the tubby mutation is a true null. We therefore generated Tub-null (Tub−/−) mice by deleting exon 3 and found that they exhibit hearing impairment like that of tubby mice, suggesting the tubby mutation is a loss-of-function mutation with regard to hearing. When we crossed Tub−/− mice with AKR mice that have wild-type Map1a alleles, we found that wild-type MAP1A restores stereocilin localization to the tips of stereocilia and rescues hearing impairment. These data suggest MAP1A does not require interaction with tubby protein in maintaining stereocilin at the tips of stereocilia and that OHCs use two independent molecules—MAP1A and tubby—to doubly ensure proper stereocilin localization.

The desire to enhance the efficiency of organic light-emitting devices (OLEDs) has driven to the investigation of advanced materials with fascinating properties. In this work, the efficiency of top-emission OLEDs (TEOLEDs) is enhanced by introducing ampicillin microstructures (Amp-MSs) with dual phases (α-/β-phase) that induce photoluminescence (PL) and electroluminescence (EL). Moreover, Amp-MSs can adjust the charge balance by Fermi level (E

We now report full details of the collisional ET process at the interface between the solvated porphyrin dye (a representative molecular dye) and heterogeneous TiO2 particles (a well-defined n-type...

Purpose: This study was performed to determine the relationship between oral-mucosal pressure ulcer (PU) stage and mechanical conditions and individual susceptibility in intubated patients. Methods: We collected 80 patient-days data from an intensive care unit of a 700-bed hospital in Korea. We analyzed oral-mucosal PUs, medical records, amount of saliva, and oral mucosal swabs. Bacterial abundance was enumerated by real-time polymerase chain reaction. The χ2 or Fisher’s exact test, t-test or Mann-Whitney U test, and Spearman’s rho correlation analysis were performed. Results: The incidence of overall oral-mucosal PUs was 31.3%, and in the maxillary and mandibular sites were 16.3% and 26.3%, respectively. There were significant correlations between the maxillary site PU stage and restraint use (r = .43, p < .001), albumin level (r = −.22, p = .046), and relative abundance of P. aeruginosa (r = .45, p < .001) and S. aureus (r = −.24, p = .033). In the mandibular sites, there were significant correlations between PU stage and restraint use (r = .30, p = .008), level of consciousness (r = .31, p = .005), and relative abundance of P. aeruginosa (r = .25, p = .028) and S. pneumoniae (r = .22, p = .046). Conclusions: Frequent monitoring and repositioning the mechanical pressure on the oral-mucosa could be an effective preventive strategy against the development and advancement of oral-mucosal PUs. Additionally, monitoring the oral microorganisms can prevent advanced stage oral-mucosal PUs in intubated patients.

Neuroinflammation is one of the most common pathological outcomes in various neurological diseases. A growing body of evidence suggests that neuroinflammation plays a pivotal role in the pathogenesis of epileptic seizures. Eugenol is the major phytoconstituent of essential oils extracted from several plants and possesses protective and anticonvulsant properties. However, it remains unclear whether eugenol exerts an anti-inflammatory effect to protect against severe neuronal damage induced by epileptic seizures. In this study, we investigated the anti-inflammatory action of eugenol in an experimental epilepsy model of pilocarpine-induced status epilepticus (SE). To examine the protective effect of eugenol via anti-inflammatory mechanisms, eugenol (200 mg/kg) was administrated daily for three days after pilocarpine-induced SE onset. The anti-inflammatory action of eugenol was evaluated by examining the expression of reactive gliosis, pro-inflammatory cytokines, nuclear factor-κB (NF-κB), and the nucleotide-binding domain leucine-rich repeat with a pyrin-domain containing 3 (NLRP3) inflammasome. Our results showed that eugenol reduced SE-induced apoptotic neuronal cell death, mitigated the activation of astrocytes and microglia, and attenuated the expression of interleukin-1β and tumor necrosis factor α in the hippocampus after SE onset. Furthermore, eugenol inhibited NF-κB activation and the formation of the NLRP3 inflammasome in the hippocampus after SE. These results suggest that eugenol is a potential phytoconstituent that suppresses the neuroinflammatory processes induced by epileptic seizures. Therefore, these findings provide evidence that eugenol has therapeutic potential for epileptic seizures.

A porphyrinic metal-organic framework (PMOF) known as PCN-222(Zn) was chemically doped with a molecular Re(I) catalyst-bearing carboxylate anchoring group to form a new type of metal-organic framework (MOF)-Re(I) hybrid photocatalyst. The porphyrinic MOF-sensitized hybrid (PMOF/Re) was prepared with an archetypical CO2 reduction catalyst, (L)ReI(CO)3Cl (Re(I); L = 4,4'-dicarboxylic-2,2'-bipyridine), in the presence of 3 vol % water produced CO with no leveling-off tendency for 59 h to give a turnover number of ≥1893 [1070 ± 80 μmol h-1 (g MOF)-1]. The high catalytic activity arises mainly from efficient exciton migration and funneling from photoexcited porphyrin linkers to the peripheral Re(I) catalytic sites, which is in accordance with the observed fast exciton (energy) migration (≈1 ps) in highly ordered porphyrin photoreceptors and the effective funneling into Re(I) catalytic centers in the Re(I)-doped PMOF sample. Enhanced catalytic performance is convincingly supported by serial photophysical measurements including decisive Stern-Volmer interpretation.

Dye detachment issue in the TiO2-mediated dye-sensitized photocatalytic system engenders an electron injection route based on collisional quenching between the detached solution-phase dye and dispe...

Herein, we report the synthesis, and photochemical and -physical properties, as well as the catalytic performance, of a series of heteroleptic IrIII photosensitizers (IrPSs), [Ir(C^N)2 (N^NAryl )]+ , possessing ancillary ligands that are varied with aryl-substituents on bipyridyl unit [C^N=(2-pyridyl)benzo[b]thiophen-3-yl (btp); N^NAryl =4,4'-Y2 -bpy (Y=-Ph or -PhSi(Ph)3 ]. We found that the π-extension of bipyridyl ligand by aryl-substitution put bipyridyl ligand in use as an electron relay unit that performed charge accumulation before delivering to the catalytic center, greatly improving the overall CO2 -to-CO conversion activities. In a typical run, the aryl-substituted IrPS (tBu IrP-PhSi )-sensitized homogeneous systems (IrPS+ReI catalyst) gave a turnover number of 1340 (ΦCO =24.2 %) at the early stage of photolysis (

Objective Despite the etiological significance of complex developmental trauma in adult personality disorders and treatment-resistant depression, neurobiological studies have been rare due to the lack of useful animal models. As a first step, we devised an animal model to investigate the effects of multiple trauma-like stress during different developmental periods. Methods Twenty-one male Sprague-Dawley rats were classified into 3 groups based on the stress protocol: fear conditioning control (FCC, n = 6), complex stress (ComS, n = 9), and control (n = 6). While the ComS experienced three types of stress (maternal separation, juvenile isolation, electric foot shock), the FCC only experienced an electric foot shock stress and the control never experienced any. We compared fear responses at postnatal day (PND) 29 and PND 56 through freezing time per episode (FTpE), total freezing time (TFT), total freezing episodes (TFE), and ultrasonic vocalization (USV). Results ComS showed the longest FTpE in the conditioned fear response test. ComS and FCC exhibited the longer TFT and these two groups only displayed USV. ComS show difference TFE between PND 29 and PND 56. Conclusion The results of this investigation show that complex stress may affect not quantity of fear response but characteristics of fear response. Longer FTpE may be associated with tonic immobility which could be considered as a failed self-protective reaction and might be analogous to a sign of inappropriate coping strategy and self-dysregulation in complex trauma patients.

In spite of recent developments in mass spectrometry imaging techniques, high-resolution multiplex protein bioimaging techniques are required to unveil the complex inter- and intracellular biomolecular interactions for accurate understanding of life phenomena and disease mechanisms. Herein, we report multiplex protein imaging with secondary ion mass spectrometry (SIMS) using metal oxide nanoparticle (MONP)-conjugated antibodies with

The reaction dynamics of a photochemical reaction is typically described by reaction coordinates based on the Born-Oppenheimer (BO) approximation. A strong interaction between electrons and nuclei, conventionally occurring at conical intersections, however, breaks the BO approximation and has major consequences for the efficiency of a photochemical reaction. Despite its importance, related studies into the non-BO dynamics are scarce. Here, we investigate the non-BO dynamics of excited-state intramolecular proton transfer (ESIPT) occurring in 10-hydroxybenzo[h]quinoline (HBQ). Two coherent vibrational modes at 237 and 794 cm-1 representing molecular dynamics on a diabatic surface in HBQ are identified by a wave packet analysis based on a transient absorption measurement with a time resolution of 11 fs and with a density functional theory-based model calculation. It is also revealed that the strong Coulomb field effect in HBQ leads to the completion of ESIPT within about two cycles of the OH stretching mode. The work paves the way for time-domain studies of molecular dynamics beyond the BO approximation in other photochemical reactions.

Highlights • The pathogenesis of MRONJ is related to repression of osteoclast mediated bone remodeling. • rhBMP-2 can stimulate not only osteoblasts but also osteoclasts and induce new bone formation. • ACS has been proved to be a good carrier of rhBMP-2 with maximal efficacy. • Application of rhBMP-2/ACS can be a new approach to surgical treatment for MRONJ patients., Introduction The purpose of this study was to pursue, and to report the results of, mandibular reconstruction and rehabilitation of medication-related osteonecrosis of the jaw (MRONJ) patients having large critical-sized defects of the mandible using a combination of recombinant human bone morphogenetic protein-2 (rhBMP-2) and absorbable collagen sponge (ACS) with surgical miniplate without any grafting materials. Case presentation Three (3) patients aged 67 and 86 (2 patients) presented due to discomfort on the mandible. They all had a medical history of bisphosphonate and steroids treatment orally or intravenously, and all had been diagnosed as MRONJ stage 3. Sequestrectomy and saucerization were performed, and then a surgical miniplate (Hansolmedical, Korea) was adapted and fixed on the sound portion of the mandible. rhBMP-2 was loaded onto an ACS at a dose of 1.5 mg/cc. Several rhBMP-2 (Cowellmedi, Korea)/ACS (Ateloplug, TRMkorea, Korea) were placed into the bony defect with a surgical miniplate. All 3 patients recovered without complications. They all exhibited radiographic evidence of bone formation by 3 months postoperatively in every case. Conclusions All 3 patients were treated successfully with rhBMP-2/ACS and miniplate without any complications. This protocol reported herein represents a new approach to the surgical treatment of maxillofacial bone defects and deficiencies, especially in MRONJ patients.

Purpose To investigate the relationship between carotid arterial calcium score (CarACS) and silent cerebrovascular lesions in patients with obstructive sleep apnea (OSA). Materials and Methods This study involved retrospective evaluation of 60 OSA patients who underwent both upper airway CT and brain MRI. Using polysomnography, several indicators, including apnea index (AI), were used to evaluate the relationship between OSA and silent cerebrovascular lesions. The CarACS was quantified on CT imaging using the modified Agatston method. Silent cerebrovascular lesions were evaluated on brain MRI by grading periventricular hyperintensity (PVH). Various clinical characteristics, including age, were analyzed in each patient. Results The number of patients per PVH grade 0, 1, 2, 3, and 4 was 26 (43.3%), 14 (23.3%), 14 (23.3%), 4 (6.7%), and 2 (3.3%), respectively. The mean age, hypertension, smoking status, AI, and CarACS were significantly different among PVH groups (Ps < 0.05). In univariate analysis, the presence of carotid arterial calcification (β = 0.483, p < 0.01), CarACS (β = 0.482, p < 0.01), and age (β = 0.360, p < 0.01) showed a significant association with PVH grade. The mean AI and lowest O2 saturation had statistically weak associations with PVH grade (β = 0.267, p < 0.01; β = -0.219, p < 0.14, respectively). In multivariate analysis, CarACS was the only factor affecting PVH grade (p < 0.04). Conclusion CarACS is associated with the severity of silent cerebrovascular lesions. Therefore, additional analysis of CarACS in OSA patients may provide more information on their cerebrovascular status.

Background The purpose of this retrospective study was to evaluate the postoperative change in the position and stability of the mandibular condyle after bilateral sagittal split ramus osteotomy (BSSRO) and BSSRO with distal segmental ostectomy (DSO) in patients with facial asymmetry using 3D computed tomography. Methods The condyles of the patient diagnosed with facial asymmetry were divided into the deviated side (DS) and the non-deviated side (NDS). Group I, which was treated with BSSRO only, and Group II, which additionally received DSO along with BSSRO, were superimposed on the condyle using the pre-and postoperative 3D CT. The amount of condylar change in anteroposterior displacement, mediolateral displacement, and rotation was measured. The clinical symptoms of temporomandibular joint were also evaluated before and after surgery for each patient. Results Between Groups I and II, there was no statistically significant difference in the anteroposterior condylar position on both DS and NDS. And also, there was no statistical difference between the two groups in the mediolateral change on DS but, statistically significant difference on NDS. The change in the rotation of the condyle was observed to rotate inward from both condylar heads of Groups I and II, and a statistically significant difference was observed between the two groups on both DS and NDS. Moreover, no difference in clinical temporomandibular joint symptoms was observed after surgery in each DS and NDS condyle of the two groups. Conclusions As a result of analyzing the condylar position change of the group treated with BSSRO alone and the group treated with BSSRO and DSO in patients with facial asymmetry, there were statistically significant differences in the mediolateral displacement of NDS and the condyle rotation of NDS and DS. However, the anteroposterior condylar position did not show any difference in the bilateral condyles. In addition, since worsening clinical symptoms of bilateral temporomandibular joint were not observed before and after surgery in both groups, it is concluded that it is not necessary to accompany DSO in patients with facial asymmetry (minimum 3 mm, maximum 7 mm).

Herein, we employed a molecular Ru(II) catalyst immobilized onto TiO

The quest to improve the performance of organic light-emitting diodes (OLEDs) has led to the exploration of new materials with properties like interfacial dipole, excitons generation, and bandgap alignment. Here, we exploit these strategies by investigating the interaction of the antibiotic ampicillin with a widely used optoelectronic material, to fabricate state-of-the-art OLEDs. The charge distribution on the ampicillin molecule facilitates the generation of an interfacial dipole with a large magnitude. The optimum fusion of the two materials provides an enhanced bandgap alignment, charge balance and J/H-aggregated excitons. Values of current efficiency (120 cdA−1), external quantum efficiency (~35%) and power efficiency (70 lmW−1) are demonstrated. The cross-evaluation of performance with penicillin devices indicates the significance of ampicillin’s specific molecular structure in improving performance. The detailed investigations demonstrate that ampicillin has superior optoelectronic properties with high potential to contribute extensively in OLEDs and photovoltaics. The need to move away from silicon-based semiconductors for the electronic industry has yielded significant developments in the use of organic materials for devices. The authors present a method to enhance organic light-emitting diodes (OLEDs) performance by adding a common antibiotic, ampicillin into a common organic semiconductor and achieving a maximum external quantum efficiency of 35%.

A series of heteroleptic iridium(III) complexes functionalized with two phosphonic acid (-PO3 H2 ) groups (dfppy IrP, ppy IrP, btp IrP, and piq IrP) were prepared and anchored onto rhenium(I) catalyst (ReP)-loaded TiO2 particles (TiO2 /ReP) to build up a new IrP-sensitized TiO2 photocatalyst system (IrP/TiO2 /ReP). The photosensitizing behavior of the IrP series was examined within the IrP/TiO2 /ReP platform for the photocatalytic conversion of CO2 into CO. The four IrP-based ternary hybrids showed increased conversion activity and durability than that of the corresponding homo- (IrP+ReP) and heterogeneous (IrP+TiO2 /ReP) mixed systems. Among the four IrP/TiO2 /ReP photocatalysts, the low-energy-light (>500 nm) activated piq IrP immobilized ternary system (piq IrP/TiO2 /ReP) exhibited the most durable conversion activity, giving a turnover number of ≥730 for 170 h. A similar kinetic feature observed through time-resolved photoluminescence measurements of both btp IrP/TiO2 and TiO2 -free btp IrP films suggests that the net electron flow in the ternary hybrid proceeds dominantly through a reductive quenching mechanism, unlike the oxidative quenching route of typical dye/TiO2 -based photolysis.

Red light-sensitized squaraine (SQ) dyes were developed and incorporated into dye-sensitized catalysts (DSCs) with the formula of SQ/TiO2/Cat, and their efficacies were evaluated in terms of performance on either water or carbon dioxide reduction. Pt nanoparticles or fac-[Re(4,4′-bis-(diethoxyphosphorylmethyl)-2,2′-bipyridine)(CO)3Cl] were used as each catalytic center within the DSC frame of SQ/TiO2/Pt (Type I) or SQ/TiO2/Re(I) (Type II). In order to convey the potential utility of SQ in low energy sensitization, the following catalytic reductions were carried out under selective lower energy irradiation (>500 nm). Type I and II showed different catalytic performances, primarily due to the choice of solvent for each catalytic condition: hydrogenation was carried out in H2O, but CO2 reduction in dimethylformamide (DMF), and SQ was more stable in aqueous acid conditions for hydrogen generation than CO2 reduction in DMF. A suspension of Type I in 3 mL water containing 0.1 M ascorbic acid (pH = 2.66) resulted in efficient photocatalytic hydrogen evolution, producing 37 μmol of H2 for 4 h. However, in photocatalysis of Type II (SQ/TiO2/Re(I)) in 3 mL DMF containing 0.1 M 1,3-dimethyl-2-phenyl-1,3-dihydrobenzimidazole, the TiO2-bound SQ dyes were not capable of working as a low energy sensitizer because SQ was susceptible to dye decomposition in nucleophilic DMF conditions, resulting in DSC deactivation for the CO2 reduction. Even with the limitation of solvent, the DSC conditions for the utility of SQ have been established: the anchoring group effect of SQ with either phosphonic acid or carboxylic acid onto the TiO2 surface; energy alignment of SQ with the flat band potentials (Efb) of TiO2 semiconductors and the reduction power of electron donors; and the wavelength range of the light source used, particularly when >500 nm.

In this study, we prepared phenylimidazole-based C^N-cyclometalated Ir(III) complexes (DMP, TPF2) and a C^C-cyclometalated Ir(III) complex (PMP), and investigated the energy transfer process by examining the intermolecular interactions between the two cyclometalated Ir(III) complexes. In films doped with 3% Ir(C^C)3 complex (PMP) and 15% Ir(C^N)3 complex (DMP or TPF2), the PMP effectively induced energy transfer to the DMP or TPF2. This intermolecular energy transfer process was investigated using a picosecond time-resolved emission spectroscopic method. In the case of mixing PMP with DMP, where two types of luminescence were observed at 470 and 580 nm, the emission at 470 nm was due to DMP, while the emission at 580 nm can be assigned as the intermolecular exciplex emission. By contrast, in the case of mixing PMP with TPF2, the emission at 465 nm corresponding to the PMP emission region decreased for 18.5 ns, while the emission at 530 nm corresponding to TPF2 increased. This emission can be attributed to...

Three phenothiazine-based A-π-D-π-D-π-A-type small molecules containing various terminal acceptor units, which act as Lewis base blocks, have been synthesized via an efficient and step-economical, direct C-H arylation strategy in the aim toward the development of hole-transporting materials (HTMs) with multifunctional features (such as efficient hole extraction layer, trap passivation layer, and hydrophobic protective layer) for perovskite solar cells (PrSCs). Optical-electrochemical correlation and density functional theory studies reveal that dicyanovinylene acceptor in SGT-421 downshifted the highest occupied molecular orbital (HOMO) level (-5.41 eV), which is more proximal to the valence band (-5.43 eV) of the perovskite, whereas N-methyl rhodanine in SGT-420 and 1,3-indanedione (IND) in SGT-422 destabilized the HOMO, leading to an increased interfacial energy-level offset. SGT-421 exhibits superior properties in terms of a sufficiently low-lying HOMO level and favorable energy-level alignment, intrinsic hole mobility, interfacial hole transfer, hydrophobicity, and trap passivation ability over spiro-OMeTAD as a benchmark small-molecule HTM. As envisaged in the design concept, SGT-421-based PrSC not only yields a comparable efficiency of 17.3% to the state-of-art of spiro-OMeTAD (18%), but also demonstrates the enhanced long-term stability compared to the spiro-OMeTAD because of its multifunctional features. More importantly, the synthetic cost of SGT-421 is estimated to be 2.15 times lower than that of spiro-OMeTAD. The proposed design strategy and the study of acceptor-property relationship of HTMs would provide valuable insights into and guidelines for the development of new low-cost and efficient multifunctional HTMs toward the realization of efficient and long-term stable PrSCs.

The high stability and strong coupling nature of gold nanoparticles (Au-NPs) than other metal counter parts have attracted the solar cell industry to pursue enhanced performances. Herein, we report on the improved performance of polymer bulk hetero-junction (BHJ) solar cells by the incorporation of large-size Au-NPs in the hole transport layer of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). To examine the reproducibility of the enhancement parameters, two different donor photoactive materials have been adapted and the role of larger-size (>70 nm, i.e. 71, 80, 87, 103 nm) Au-NPs in BHJ solar cells have been studied extensively. Significantly, when employing Au-NPs smaller than 80 nm, near-field coupling (localized surface plasmon resonance; LSPR) was prevalent, while the infusion of Au-NPs with sizes greater than 87 nm resulted in far-field scattering enhancement as the dominant effect, which was clearly determined using time resolved photo luminescence studies. The superior power conversion efficiency of 5.35% and 8.58% was achieved with PBDTTT-C: PC61BM and PTB7: PC71BM BHJs respectively, by employing 87 nm Au-NPs due to the balanced contribution of near- and far-field plasmonic effects, improved vertical coverage and better interfacial properties. This study illustrates that 87 nm Au-NPs is the maximum size to attain the improved efficiency, above which the rate of enhancement reduces dramatically.